Treatment of phosphorus



Patented May 14, 1940 2,200,742 TREATMENT OF PHOSPHORUS Charles Hardy, Pelham Manor, N. Y., assignor to Hardy Metallurgical Company,

New York,

N. Y., a corporation of Delaware No Drawing. Application November 21, 1938. Serial N0. 241,509

Claims.

This invention is concerned with the treatment of elemental phosphorus and its incorporation in metallic bodies. More particularly, the invention is concerned with. incorporating phosphorus 5 into bodies of metals with which phosphorus tends to react exothermically, and aims to accomplish the incorporation in such a way that w the elemental phosphorus becomes substantially stable at ordinary temperatures, but is free at least in part to react exothermically with the metal when the body containing both is raised to a more elevated temperature. The exothermic heat of reaction thus may be conserved and usefully employed in alloy manufacture, welding and other metallurgical processes in which phos-, phorus is combined with metals.

Phosphorus occurs in three allotropic forms, red, yellow and black. The yellow form melts at about 44 C. and boils at about 280 C. The yellow and black forms oxidize so readily that they ignite spontaneously in air. The red form oxidizes in air at ordinary temperature but not so rapidly as to cause spontaneous combustion. Phosphorus is a valuable alloy ingredient with some metals, for example, in phosphor-bronze. It also aids in imparting fluidity in welding and similar processes where ready flow of metals is desirable or requisite, and because of its afiinity for oxygen is useful as a deoxidizer in many metallurgical processes. However, elemental phosphorus, even in the relatively stable red form, is difficult to employ in pyrometallurgical processes because of the ease with which it oxidizes. Moreover, the ease with which phosphorus 5 is oxidizedmakes it difficult and sometimes dangerous tostore. Consequently, it has been proposed heretofore to utilize phosphorus in metallurgical processes while combined with metals in the form of phosphor metals or metallic phosphides. Such forms of phosphorus generally are stable, probably because in the case of many metals, formation of alloys or phosphides is accompanied by a release of considerable heat,

which must be restored in order to reverse the process of formation.

Heretofore customary practice employing phosphor metals as welding agents has involved supplying heat to the metals in amount sufficient to raise them above their melting points so that they fuse and bring about bonding of metallic surfaces between which they are interposed. For example, a eutectic alloy of phosphorus and copper containing about'l.3% of phosphorus and having a melting point of about 710 C. has been employed heretofore as a welding agent and brings about adequate bonding between various non-ferrous surfaces, provided that the welding operation is conducted at a temperature high enough to bring about fusion of the eutectic and at least incipient fusion of the surfaces to be 5 welded together. Thus, in a present day continuous brazing operation wherein lengths of copper tubes or bars having a melting point of about 1080 C. are welded end to end as they pass through a heating zone with eutectic phos- 10 phor copper (melting .point 710 C.) in contact with the joint to be welded, the heating zone is maintained at 850 C. to assure that the melting point of the eutectic is exceeded. In the practice of my invention equivalent results are obtained while maintaining the heating zone at substantially lower temperatures.

As a result of my investigations, I have discovered that at temperatures below those at which elemental phosphorus alloys or combines 20 with a metal, it tends to penetrate or diffuse into fine particles of the metal so that, in effect,

a phosphorus-containing layer is formed thereon. This layer or coating is stable under ordinary conditions and the phosphorus contained therein 25 is protected from oxidation. .The stability thus achieved appears to be due to the fact that the fine metal powder particles adsorb phosphorus.

If the metal which adsorbs the phosphorus is one with which phosphorus tends to be com- 30 bined exothermically, such exothermic combination may be brought about subsequently by heating the treated metal particles to the point at which the exothermic heat of combination of the metal with phosphorus is released and therefore 35 usefully employed. My invention, therefore, contemplates a novel metallurgical addition agent for use in alloy manufacture, welding or the like i (and especially as a welding composition) comprising finely-divided particles of a metal with which phosphorus tends to combine exothermically, said particles also containing phosphorus which is in the free state (i. e., not combined as a phosphide or alloyed with the metal) but sufiiciently stable by virtue of its intimate association with the metal that it is substantially non-oxidizable under atmospheric conditions.

In the process of my invention (as described and claimed in my co-pending application, Serial No. 242,601, filed November 26, 1938), the metal- 50 lurgical addition product is made by treating powder of a suitable metal, in a substantially uncompacted condition, with elemental phosphorus, the treatment being carried on above the melting point of yellow phosphorus but substantially below the temperature at which exothermic combination of the metal and the phosphorus is completed, and preferably below the temperatures at which said combination begins. Any metal which will combine exothermically with elemental phosphorus at temperatures above the melting point of yellow phosphorus may be employed in the practice of my invention, among such metals being platinum, zinc, nickel and cobalt, which tend to combine with phosphorus with generation of heat and light, and sometimes, as I have discovered in the case of nickel, with almost explosive violence. Silver, gold, copper, lead, cadmium and tungsten, whose combination with phosphorus is attended by the liberation of heat only, may also be employed. The combination may be either by way of solution or reaction. In other words, the exothermic heat of combination may be either a positive heat of solution or of reaction, or both. From a commercial standpoint, compositions of my invention in which one or more of the metals, copper, cobalt and nickel, are included with free stable phosphorus are probably most important and hereinafter my invention is described in detail with reference to these elements. It will be understood, however,

that my invention contemplates broadly the manufacture of a metallurgical addition agent by exposing to the action of elemental phosphorus the powders of a metal with which phosphorus tends to combine exotherm'ically (eitherbyalloying or reacting therewith) the treatment of the metal powder with the phosphorus being conducted under such conditions that combination of the metalwith the phosphorus is inhibited to the end that the phosphorus acquires stability at ordinary temperatures, but is free to combine with the metal at more elevated temperatures with a release of exothermic heat. As explained more fully hereinafter, my'invention also contemplates the improvement ina process (for example, welding or alloy manufacture) involving the incorporation of phosphorus into a body of metal, which comprises adding phosphorus to said body in the form of finely-divided metal powder, the individual particles of which contain free phosphorus and a metal capable ofreacting exothermically with the phosphorus, and heating said mixture in contact with said body untilthe metal and the phosphorus combine exothermically. These and other features of my invention will be understood more thoroughly in the light.

of the following description of the presently preferred manufacture, nature and utilization of the novel metallurgical addition agents of my invention.

, At atmospheric pressures finely-divided copper temperature range of from 44 C, to 135 C. Yellow phosphorus boils at 280 C. so that the treatment may be accomplished either with molten or vaporized phosphorus. However, from, the standpoint of conserving the heat of exothermic combination, treatmentwith phosphorus in the liquid state is preferred.

spontaneously, is not easy to mix with metal powder, I prefer to employ this variety of phosphorus by vaporizing it.- I have found, however, that the stability-of all forms of phosphorus is improved merely by mixing them with a substantially large proportion of metal powder of high heat conductivity and without the application of heat. Phosphorus in such a mixture does not ignite spontaneously in air, and its rate of oxidation is substantially reduced. I attribute the prevention of spontaneous combustion to the fact that the metal powder particles protect the surface of a. large proportion of the phosphorus from the actionof air and thus reduce the amount of heat generated by oxidation, and also to the fact that such heat of oxidation as'is generated is conducted out of the mass with such facility that the phosphorus does not rise to ignitiontemperature. Whatever be the explanation, I have discovered that mere mechanical mixtures of elemental phosphorus and alarge proportion of metal long periods 'in air with but slight danger of substantial oxidation-and'substantially none of spontaneous ignition, and my invention contem plates the protection of phosphorus from oxidation by such means.

Assuming that the phosphorus to be employed is of the red variety and isinpowdered form, the procedure which I prefer to employ is as follows: Powdered redphosphorus and metal powder, for exarnpla-copper, in the proportions which are desired in the product, are mixed together at room temperature. On a small scale, mixing may be accomplished by introducing the requisite amounts of the ingredients, say 10 parts by weightof powdered red, phosphorus, and 90 parts by weight of copper powder into a glass bottle which is a few minutes until the mixture appears homogeneous when viewed with the naked eye. Mixingupon a larger scale may beaccomplished in a closed rotating-mixing 'drum lined with wood or lead orsimilar material which does not tend to cause sparks. The resulting mixture: usually is subjected toheat treatment soon after preparation, but if necessary may be kept for a con-. siderable period without taking any special precautions against oxidation.

Generally speaking,'the-finer the metal powder the more intimate the mixture with the phosphorus and the more rapid'the rate at whichphospowder may be stored for 35 then corked and rolled or shaken for phorus penetrates the metal powder particles I place under non-oxidizing conditions. These may be obtained by filling the container in which the heating is to with the mixture,

occur substantially completely by evacuation of the container,

or by filling the voids therein with a nonoxldizlng gas, such as nitrogen or hydrogen.

The powder mixture should be heat treated while in a substantially uncompacted condition. The use of pressure tends to cause combination of the phosphorus with the metal. The uncompacted mixture of phosphorous powder and metal powder should be heated, preferably in a closed crucible, to assure melting of the phosphorus.

The penetration of phosphorus into the metal powder appears to be most rapid at temperatures slightly below the boiling point of phosphorus, say 271 C., but with certain metals, for example, copper, exothermic combination sets in before this temperature is reached, and with such metals the, optimum treatment temperature is just below that at which exothermic reaction sets in. In the case of copper, this temperature is about.130i C. With certain other metals and metal mixtures, such, for example, as'ni'ckel', the

exothermic combination is not appreciable at temperatures below the boiling point of phosphorus, and withsuch metals, treatment at about 271 C. is optimum.

After a short heating interval, say 30 minutes, at an appropriate temperature, the heat treated mass is allowed to cool in a non-oxidizing atmosphere and will in general be found slightly consolidated. However, the particles may be broken apart by a mild crushing action. Ordinarily, the degree of consolidation is so slight that a relatively vigorous screening operation will serve to break up the aggregates, although to assure the absence of any aggregates, it may be desirableto subject the heat treated mass to ball milling or the like.

To take a specific example of the practice of my invention for the manufacture of a weldin composition containing optimum proportions of phosphorus, 7.3 parts by weight of powdered red phosphorus are mixed with 92.7 parts by weight of copper powder having a particle size of 20 mesh or less, and in which the copper particles are substantially unoxidized. Mixing is accomplished by rolling in a sealed glass-lined drum for about 20 minutes. The mixture is then placed in a sealed muffle in a reducing or non-oxidizing atmosphere of flue gas or hydrogen, heated to a temperature of 130 C., and maintained at this temperature from 30 to 60 minutes. The mass is then allowed to cool in a non-oxidizing atmosphere and after cooling, subjected to slight comminution (for example, by rolling between the hands) in order to restore all of it to powder form. After such treatment, the mass consists of finely-divided copper particles having a decreasing phosphorus content which tends to be of highest concentration at the surface of the particles and to decrease with depth. The particle size of the product is substantially that of the original copper powder, and the phosphorus content is about 7.3%. Because the operation is carried on in a closed vessel, losses of phosphorus are negligible.

As indicated hereinbefore, the foregoing procedure, with modifications, may be employed when the phosphorus is of the yellow or black variety. But with these less stable varieties of phosphorus, which are also more difficult to mix because of their pasty condition, mixing should be conducted in an evacuated or nonoxidizing atmosphere. For instance, pasty yellow phosphorus may be pugged with dry nickel powder in a pug mill from which air is excluded phorus can occur on and in which the moving parts are of a nonsparking material such as wood. In general, however, it is more convenient both from the standpoint of safety and ease of operation to vaporize the yellow or black phosphorus and bring it into contact with the metal powder in such condition, provided, of course, that the particular metals do not combine with complete liberation of exothermic heat at the temperature of treatment. Preferably, the phosphorus is vaporized and passed in contact with the metal powder particles heated to the point where phosphorus will condense upon the powder particles as a liquid but not as a solid. Intimate contact between the metal powder and the phosphorus may be assured by permitting the metal powder particles to pass in a dispersed condition through a body of the phosphorus vapor (so that in effect, the phosphorus vapor is passed through a mass of the metal powder) or by agitating the powders in contact with phosporus vapor. Good contact may also be obtained by forcing the phosphorus vapor through a relatively thin bed of the loose metal powders. In most cases, adequate contact may be assured merely by passing the phosphorus vapor over a relatively thin bed of the metal powders.

The heat contained in the metal powders and the phosphorus vapors brought into contact with each other should be sufficient to prevent the condensation of thephosphorus on the particles as a solid, i. e., under such conditions that the phosphorus does not freeze on the particles. Optimum conditions are established when the total heat in the powdered particles and vapor is just insufficient to permit phosphorus to remain in the vapor state so that at least some of it condenses as a liquid on the particles. In other words, the heat in the phosphorus powder and the metal particles should be such that the resulting mixture has a temperature just below the dew point of the phosphorus, However, good results are obtained at higher temperatures at which no condensation of phosthe metal particles provided that the temperature does not rise to the point where exothermic combination is completely released.

A simple practice of the inventionwith phosphorus vapor may be carried out as follows:

An alundum boat or the like containing a relatively thin layer of clean metal powder (for example, nickel powder with substantially unoxidized surfaces and of particle size ranging from 100 to 200 mesh) is placed in a muflle provided with means for passing phosphorus vapor thereinto in a non-oxidizing atmosphere. By cooling, the phosphorus may be caused to condense as a liquid on the powder metal mass. If the surface of the metal powder particles is oxidized, it is desirable to remove this through preliminary contact of the heated powders with a reducing gas, for example, dry hydrogen. Thus, the powder may be heated in the muffle to a temperature of about 300 C. while dry hydrogen is passed therethrough so as to remove any coating of oxide or the like from the metal and any oxygen that is entrained in the metal powder mass. After non-oxidizing conditions are established, phosphorus vapor from any convenient source is admitted into the mufile and passed over the heated metal powder until the requisite amount of phosphorus has been adsorbed in the mass. Thus, phosphorus vapor at 300 0. passed over a layer of copper powder about inch thick and maintained at a temperature of about 270" C.

results in the formation of a suitable metallurgical addition agent containing about 10% by weight of phosphorus after about 30 minutes.

Ordinarily, conditions of such that substantially all condensed as however, residual phosphorus is contained in the exit gases from the muffle, this may be condensed separately and returned to thesource of phosphorus vapor or circulated in vaporized condition back through the mufiie.

In a more elaborate modification of thepractice of my invention with phosphorus vapor, the latter is passed. in countercurrent contact with metal powder in a first zone in which the temperature is too high to permit substantial condensation of phosphorus vapor andin a second zone in which the temperature is low enough to operation should be of the phosphorus is this way, substantially, all of the phosphorus is caught in the second zone, but the product withdrawn from the first zone has been heated so high that any unstable elemental phosphorus contained on the particles is vaporized. In such practice, the temperature of {the first zone could be substantially below that at which exothermic combination between the'metal powder and the phosphorus occurs.

' The foregoing modification is adapted to a continuous operation in which the metal powder to be treated with phosphorus is firsts'ubjected'to treatment in a cleansing chamber to remove ,moisture and entrapped gases of an oxidizing nature, and (when necessary) to remove solid oxidation products from the surface of the powder particles. Cleansing in the chamber is, accomplished by treating the metal powders therein with a hot, non-oxidizing and preferably reducing gas. Thus, the metal powder may fall through the cleansing chamber in a dispersed condition in'countercurrent contact with a rising current of 'flue gas containing suflicient' carbon monoxide to convert any oxygen entrained in the powder to carbon dioxide, and the gas should be hot enough to permit such a reaction to occur. If reduction of solid products of oxidation on the surface of the particles is necessary in order to expose clean metal for subsequent contact with phosphorus, hot gas containingsubstantial quantities of hydrogen may be employed.

The cleansed metalpowder from the cleansing chamber (while protected against exposure to the air) is conducted into a phosphorus treatment chamber whereit passes in countercurrent contact with phosphorus vapor. Thus, the metal powder in a dispersed condition may fall through a rising stream of thefphosphorus vapor in the chamber, the topflof the chamber being maintained at a temperature low enough to assure the condensation of substantially all of the phosphorus as a liquid, and the bottom of the chamber being maintained at a temperature high enough to volatilize any unstabilized phosphorus on the metal particles entering this zone,,the treated metal powder particles being withdrawn from the bottom of the chamber, cooled under non-oxidizing conditions to room temperature, and thereafter subjected to a mild crushing, action, if necessary, to separate any metal particles that may have become cemented together during the treatment with phosphorus. I

With a view toward controlling the rate at which phosphorus is adsorbed by the metal powa liquid on the metal powder. If,

dition agent whenever passing through the ance copper is employed the metal powder may be diluted with a non-oxidizing or reducing gas, for example, dry nitrogen. This lowers the concentration and vapor I pressure of the phosphorus and reduces the rate at which it is adsorbed. Dilution, however, requires complexities of apparatus and procedure which usually are not justifiable from an economic standpoint, and ordinarily it is advisable toemploy substantially undiluted phosphorus vapor.

Penetration of phosphorus into the metal particles is more profound and the phosphorus content of the particles more uniform as the time of heat treament is increased. I

As indicated hereinbefore. the product of my invention is suited for use as a metallurgical adit is desired to add to a metallic body, both phosphorus and the metal .-with which it is included in the product and with I which it tends to combine exothermically at ele permit the phosphorus to condenseto liquid. In

vated temperatures.

7 a copper and phosphorus may be added to metal which is to be made into phosphor-bronze by a process involving fusion. Upon heatingthe product in contact with the metalflto an elevated temperature, exothermic heat of combination is usefully to aid in melting. Thethermal economies thus brought about 'are considerable.

In welding 'processesand especially in welding processes in which the article to be welded is passed through a heating zone maintained at a temperaturehigh enough tofinsure the heating of the article to the welding point while zone, my, invention affords great heat savings and moreover, permits weld ing to be accomplished in a zone maintained at substantially lower temperatures than employed heretofore, despite the fact that the surface of the member, to be welded is-heated as high or higher than in'heretofore customary operations. In other words, when employing the welding composition of my invention, ordinarily it is only necessary to raise the points to be welded to the temperature at which exothermic combination of the elements in the welding composition becombination being suflicient 'to bring about fusion of the welding composition and to raise the metal surfaces to be joined to welding heat. This may be illustrated by contrasting thebutt-welding operation'of copper members described hereinbefore with the operation in which the welding composition of my invention containing 7.3% phosphorus and the balinstead of a true phosphorus-copper alloy of eutictic composition. In accordance with my invention, copper-phosphorus powder pmade as described hereinbefore and containing 7.3% phosphorus is placed in the joint to be welded with a suitable flux, for example, borax or sodium silicate, and the joint is passed slowly through the heating zone maintained at a temperature which may be as low'as 650 C. Asv the temperature. of the joint is raised, there is a sudden evolution of heat which aids in the welding. In heretofore customary operations employing phosphor-copper alloy containing the same proportions of phosphorus, it is required that the heating zone be maintained at temperatures in the neighborhood of 900f C. In contrast, adequate welding is, obtained in accordance with my invention when the zone is heated toa point substantially below the meltf ing point of the lowestmelting phosphor-copper alloy, 1. e., the eutectic.

For welding stainless steel, I have found that a released and is employed suitable welding composition is made-from a mixture ofmetal powder containing eopper, nickel .andtin in theproportions of about 50:35:10 by weight. Intoa ,dry, uncompressed mass of this powder mixture there is intimately incorporated 5% by weightof powdered red phosphorus. Then -,the mixtureis, heated under non-oxidizing conditions to a temperature of about 270 0;, maintained at this temperature for about 30 minutes,

and then cooled immediately under non-oxidiz- V i ing conditions. mixture to powder state and the productv is then Mild comminution restores the readyfor use in welding stainless steel. A convenient practice in welding stainless sheets and the like of the familiar 18 and 8 variety is' to press a layer of this welding composition between the members which form the joint by clamping the members together. (A flux, suchas borax or sodium'silicate may bemixed with'the composition if desired but is not necessary when the joint is compressed in this manner.) i The joint then is heated to a temperature of at least '600" C. whereupon adequate welding ensues. Compression aids in accomplishing welding at this low temperature and also makes it unnecessary to employ fluxes or a special non-oxidizin atmosphere; because' the welding composition is protected from oxidation within the joint The weld. formed in the above-describedprocedure is practically as corrosion-resistant as the orig inal stainless steel, probably becauseofthe corrosion-inhibiting properties of the nickel incorporated into 1 the weld. t

. My invention is by no means restrictedto the foregoing examples because welding compositions capable of releasing heat may be formedwith phosphorus and a variety of metals. The critical temperature below whichthe welding composition of my invention should be formed and above which it tends to release its exothermic hea't depends upon the particular'metalor metal mixture employed. "The critical temperature may be determined in any instance' by slowly I'heating a mixture of red phosphorus with the powder'of the particular metal being investigated in a non-oxidizing or reducing atmosphere while conducting pyrometric'observations of'themixture. A thermocouple may beembedded in the mixture. It

will be found that there is a sudden evolution of heat whena mixture is brought into a certain temperature range. The critical temperature range for various metals and metal mixtures has been determinedexperimentally and is reported below.

I Critical temperature Mixture range, s

Metallic ingredients, perisg g Heat evolu- Heat evolueent by weight phospholius tlon begins tron ends Gil-92 8 $135 +370 Ni-89 ll 1425 +810 PIP-95 5 i425 +555 (Eu-50; Ni-Iifi; Sn5 5 5:385 +790 C0-88.5 ll. 5 i380 +910 It is diilicult to determine in all instances whether the exothermic heat of combination generated by the phosphorus and the metal or metals is one of solution or reaction. This, however, is immaterial from a practical standpoint since the object is to utilize the heat irrespective of the particular physico-chemical action by which it is derived.

The amount of phosphorus to employ will deditions.

upon the amount .of phosphorus to incorporatein the welding pend chiefly which it is desired or other metallurgical operation for which the metallurgical additionagent of my invention is designed. Generally speaking, the phosphorus 5 content of the addition agent may correspond with the phosphorus Lcontent of the metallic phosphides' and alloys heretofore customarily employed. In the case of the agent made fromphosphorus and copper composition,' the phosphorus content should range from 5 to 10% by weight, a phosphorus content corresponding to eutectic composition,

i. e., 7.3% 'byweight-being preferred. However,

and employed as a welding 10 a much higher phosphorus content maybe incorporated in the copper and still'forma stable composition. I have incorporated successfully as much as 40% by weight of phosphorus in the copper according to the process of my invention and haveachieved a composition which is to all ill) and purposes stable in atmospheric conintents When the metallurgical addition agent of my invention is employed as a substitute for a master alloy for incorporatingphosphorus into phosphor-bronze and the like, it may be desirable to employ a relatively large proportion of. phosphorus in the mixture, say upwards of 15%;

The metallurgicaladdition agent of my invention should be employed in substantially-theeonit should not be consolidated under'highfpres- "sure or' atelevatedtemperatures because of the danger of loosing 'and losing the exothermic heat. However, if a massive form of an addition agent ditionin which it was formed. In otherwords, a0

is desired, for example, a welding/rod, the loose powder particles or the additionagent. may be bonded together with an extraneous substance which does not interfere in the operation for whichthe mass is intended. In the'case of, welding rods and the like, the bonding agent employed 4;

may be a flux havingbondingproperties, forexample, sodium silicate. Similarly, 'in the manufacture of phosphor-bronze, the addition agent I of my invention may, prior to use be briquetted under mild'pressure and temperature with a M suitable fluxlngjagent or'eve'n'with a carbonaceous binder such as tax oi-molasses which will burn or volatilize at the temperature of manufacture. Generally speaking, any oi the fluxes which have been employed heretofore in-melting or welding operations for a particular metal or metal mixture may be employed in the practice of my invention. The use of fluxes having a strong oxidizing action should be avoided for the reason that these tend to affect the phosphorus.

The addition agent of my invention may be used as a welding composition in any of the heretofore customary types of welding. In the acetylene or arc welding processes, the powder may be bonded together and employed in a form of a rod or an electrode if desired, but ordinarily will find application as unbonded powder. In pressure welding, as described hereinbefore with reference to stainless steel, bonding results from merely compressing a layer of the powder between the surfaces to be welded and heating the joint to the powder at which exothermic combination and consequent fusion occurs. In some instances, for example, with a composition made from nickel and phosphorus, mere pressure will generate sufiicient heat to bring about the exothermic combination and resulting welding.

I claim:

1. A metallurgical addition agent capable of generating heat at elevated temperatures but sub- 15 I tendsto react exothermically with-phosphorus,

powder containingadsorbed freephosphorus. 3. -A metallurgical. addition agent capableof generatingheat at elevated-temperatures but substantially stable under atmospheric conditions which comprises the powder of,a-me,tal which the. particles of; said powder-. being penetrated by -1ree phosphorus;v 4

4 A metallurgical addition, agent capable of generating heat at elevated temperatures which comprises a, metal selected from the groupconsistin'g, of '-platinum, zinc, nickel}; cobalt, silver,

powder; the parti '9. A welding compo sition which finely divided mass having individual particles gold,zcopp er, lead, cadmium and tungsten in pow- .der forin and having particles containing. diffused .free phosphorus. h I g ,b. A: metallurgical addition agent capable- 0f,

generating. heat 'at elevated temperatures but substantially stable at 1 ordinary temperatures which comprises a metal inpowder form and selected from the group consisting-of platinum, zinc,

nickel cobalt, silver,,gold, copper, lead cadmium and tungsten, the taming-free phosphorus.

J 6. A vweldingcornposition which comprises copers, the particles of which, contain, ad-

sorb'ed nee phosphorus.

7. A welding ,composition -which comprises a powder containingthe metals coppen niclgel, and tin in aboutlthe proportionsv 50, 35,10, and phos phorus, a substantial part of the phosphorus being 'fr'ee tocombine exothermically. with the .metals.

8. A w elding composition which comprises a copper andphosphoruswhich is free .t exothermically with thecopper.

comprises a containing both free phosphorus and a metal capable of reacting exothe initially, with said: free phosphorus."

a 1.0. In a" metallurgical processinvoivingthe incorporation of phosphorus into a metallic body,

; pable 10f; reactingv thermically.

particles of said powder conphosphorus; and a es of which contain metallic combine 2,200,742 ;;stantially stable under atmospheric conditions;

and comprising the powder of a metal with which vphosphorus tends to combine exothermically,i the particles of the: powder containing difiusedirce phosphorus.v r i 1 2-.-=A -.metallurgical addition agent capable .of generating heat at elevated temperatures but substantially stable under .a 'tmospheric conditions 'which'comprises the powder ofa-metal with which phosphorus tends to combineexothermic'ally. said phorus to said body in-the form of finely-divided metal powder-having individual particles containing both-free phosphorus'and a metal capable of reacting exothermically with the phosphorus,

and heating said' metal pow der in contact-with saidbody until exothermic reaction sets-in between the. phosphorus and-the metaLf z-llglna metallurgicalfprocess involving the incorporation of phosphorus intoa metallic body,

the improvement which comprises adding I phosuntil thegmetal and the improvement which comprises adding phos- -phorus.tosai'd body. in the form of apowder mixture containing :free phosphorus and a. metal caexothermicall-y" therewith and heating said mixture in contact with 'said body the phosphorus combine exoj}-1 2.-I1"1"a metallurgical process involving the incorporationzof phosphorus into a metallicbody, the improvement-which comprises addingtothe" bo fi e divided particles of a metal capable of combiningqexothermically with-coppensaid particles having a coating containinggfree phosphorus; and heating said particles in contactwith said vbody until themetal and :the phosphorus combine exothermically, I

1 3 In a 'metallurgical process involving the incorporation of, phosphorus into ametallic body,

binee rothermicallyg,with phosphorus. at relatively .high temperatures, i said particles having free r the; improvement which comPrisesadding'to the bodythe powder of a me'tal which tends tocomphosphorus adsorbed therein and .heating said particlesin contact with the body until the. metal combines exothermicallywith thephosphorus.

generating heat at eleyatedtemperatures but substantially stable under atmospheric; conditions and comprising the powder-of a metal with which phosphorus tends to combine exothermically, the

particles of t e powder containing diffused free mixedw ith' saidparticles of metal powden; g 15. A. metallurgical addition agent capable of generatingheatjat elevated temperatures but substantiallystable under atmospheric conditions and comprising the powder of .a metal with which fluxin'glagent intimately adphosphorus tends to 'combinerexothermically, said powder containing adsorbed freephosphorus and being bonded together-by ailuxing agent; H

ifbniijams m 14 .,A.meta llurgica1addition, agent capable of 

